Azo compounds

ABSTRACT

The present invention relates to novel dyestuffs of formula (I) wherein the substituents have the meanings defined in the claims, the production of such dyestuffs, the use of these dyestuffs and material dyed or printed by such dyestuffs.

The present invention relates to novel disperse dyes, to theirpreparation, and to the use thereof for dyeing and printing regeneratedor synthetic hydrophobic materials and/or blends comprising regeneratedor synthetic hydrophobic materials.

The present invention relates to novel dyestuffs of formula (I)

wherein

-   -   X signifies H; halogen, preferably Cl or Br; —CN; —SO₂CH₃; —OH;        —OCH₃ or —NO₂,    -   Y signifies H; halogen, preferably Cl or Br; or —CN, and    -   K signifies a coupling component radical of the        6-hydroxypyridone-2, aniline, α-naphthylamine, 5-aminopyrazole,        5-hydroxypyrazole, indole, tetrahydrochinoline, 2-aminothiazole,        2-aminothiophene, phenole which is not 3,5-dimethyl substituted        and the substituents in the 3 and 5 position are not members of        a second ring, 2-naphthol, benzomorpholine or        2,6-diaminopyridine series.

In formula I, preferably

-   -   X signifies H; halogen, preferably Cl or Br; —CN, or —NO₂,    -   Y signifies H; halogen, preferably Cl or Br; or —CN, and    -   K signifies a coupling component radical of the        6-hydroxypyridone-2, aniline, α-naphthylamine, 5-aminopyrazole,        5-hydroxypyrazole, indole, tetrahydrochinoline, 2-aminothiazole,        2-aminothiophene, 2-naphthol, benzomorpholine or        2,6-diaminopyridine series.

More preferred coupling component radical K are of 5-hydroxypyrazole,6-hydroxypyridone-2 or aniline series.

More preferred coupling component radical K are of the6-hydroxypyridone-2 or aniline series.

The most preferred coupling component radical K is of the5-hydroxypyrazole serie.

Particularly preferred are dyestuffs of formula (I-A)

wherein

-   -   X signifies H; halogen, preferably Cl or Br; —CN, —OH; —OCH₃ or        —NO₂,    -   Y signifies H; halogen, preferably Cl or Br; or —CN, and    -   R¹ signifies C₁₋₆-alkyl; substituted C₂₋₄-alkyl, preferably        substituted by one or more substituents of the group consisting        of halogen, —CN, —SCN —OC₁₋₄-alkyl, —OCOC₁₋₃-alkyl, —OCHO,        —OC₆H₅ and —C₆H₅; C₃₋₄-alkenyl; substituted C₃₋₄-alkenyl,        preferably substituted by —Cl or —Br; C₃₋₄-alkinyl, preferably        propargyl; C₂₋₄-alkylene-OCO—C₁₋₃-alkyl;        C₂₋₄-alkylene-O(CO)O—C₁₋₃-alkyl; C₁₋₃alkylene-COO—R⁵;        —C₁₋₃-alkylene-COO—C₂₋₃-alkylene-N-phthalimid;        C₁₋₃-alkylene-COOCH₂COOR⁵ or C₁₋₃-alkylene-COOCH₂COR⁶,        -   wherein R⁵ signifies C₁₋₄-alkyl; C₁₋₂-alkoxyethyl;            C₃₋₄-alkenyl; C₃₋₄-alkinyl; cinnamyl; phenoxyethyl;            phenyl-C₁₋₃alkyl; tetrahydro-furfuryl-2; phenyl or phenyl,            which is substituted by —CH₃, —OCH₃, —COOCH₃ or —COOC₂H₅,            -   R⁶ signifies C₁₋₄-alkyl; phenyl or substituted phenyl,                preferably substituted by one or more substituents of                the group consisting of —CH₃, —OCH₃, —OC₂H₅, halogen and                —OH,        -   R² signifies H; C₁₋₆-alkyl; substituted C₂₋₄-alkyl,            preferably substituted by one or more substituents of the            group consisting of halogen, —CN, —OH, —OC₁₋₄-alkyl,            —OCOC₁₋₃-alkyl, —OC₆H₅ and —C₆H₅; C₃₋₄-alkenyl; substituted            C₃₋₄-alkenyl, preferably substituted by —Cl or —Br;            C₃₋₄-alkinyl, preferably propargyl;            -   C₂₋₄-alkylene-OCO—C₁₋₃-alkyl or C₁₋₃alkylene-COO—R⁵,    -   R³ signifies H; CH₃; —NHCO-A¹ or —NHCOO-A²,        wherein        -   A¹ signifies H; C₁₋₄-alkyl; C₂₋₃-alkenyl; phenyl; —NH₂ or            substituted C₁₋₂-alkyl, preferably substituted by one or            more substituents of the group consisting of —OH, —Cl,            —OCH₃, OC₂H₅ and —C₆H₅,        -   A² signifies C₁₋₄-alkyl or substituted C₂₋₄-alkyl,            preferably substituted by one substituents of the group            consisting of —Cl, —OCH₃ and —OC₂H₅, and    -   R⁴ signifies H; halogen or C₁₋₄alkoxy,    -   as well as mixtures thereof.

Further particularly preferred are dyestuffs of formula (I-B)

wherein

-   -   X signifies H; halogen, preferably Cl or Br; —OH; —OCH₃ or NO₂    -   Y signifies H,    -   R⁷ signifies H; benzyl; phenyl; C₁₋₆-alkyl; substituted        C₂₋₄-alkyl, preferably substituted by one substituent of the        group consisting of halogen, —CN, —OH, —OC₁₋₄-alkyl,        —OCOC₁₋₂-alkyl, —OC₆H₅ or —C₆H₅; —C₁₋₂-alkylene-COOC₁₋₂-alkyl;        —NHC₆H₅ or —NH₂,    -   as well as mixtures thereof.

Further particularly preferred are dyestuffs of formula (I-C)

wherein

-   -   X signifies H; halogen, preferably Cl or Br; —OH; —OCH₃ or NO₂;    -   Y signifies H,    -   R⁸ signifies H; C₁₋₆-alkyl; cyclo-hexyl; phenyl; substituted        phenyl, preferably substituted by one substituent of the group        consisting of halogen, —CH₃, —CN, —OH, —OC₁₋₄-alkyl,        —OCOC₁₋₂-alkyl, —COC₁₋₂-alkyl, —COOH, —SO₂C₂H₄OH or —NO₂    -   R⁹ signifies C₁₋₄-alkyl; phenyl or —CF₃,    -   as well as mixtures thereof

Any alkyl present is linear or branched unless indicated to thecontrary.

Any substituted alkyl present can be optionally substituted by one ormore identical or different substituent.

Halogen atoms are preferably chlorine or bromine.

The above-mentioned novel compounds as well as mixtures thereof are veryuseful disperse dyestuffs.

Production of these dyestuffs is effected by coupling a diazotized amineof formula (II)

wherein all substituents have the meanings given in anyone of thepreceding definition in the description is coupled with an amine offormula (III)H—K   (III)wherein all substituents have the meanings as defined above.

For the preparation of the cyano derivatives of compound (I) a furtherstep may comprise the partially or complete cyanation of the bromoderivatives of the compound according to formula (I) wherein X and/or Ysignifiy —Br.

Diazotization and coupling are effected by generally known processes.

The diazotization is carried out, for example using sodium nitrite inacid aqueous medium. The diazotization can also be carried out usingother diazotization agents, for example nitrosyl sulfuric acid. Anadditional acid may be present in the reaction medium duringdiazotization, for example phosphoric acid, sulfuric acid, acetic acid,propionic acid, hydrochloric acid or mixtures of these acids, e.g.mixtures of phosphoric acid, and acetic acid. Diazotization isconveniently carried out within the temperature range of from −10 to 10°C., preferably from 0° C. to 5° C.

Coupling of the diazotized compound of formula (II) to the couplingcomponent of formula H—K (III) is carried out in known manner, forexample in acid, aqueous or aqueous-organic medium, preferably withinthe temperature range from 0° C. to 50° C., more preferably from 10° C.to 20° C. Acid used are, for example hydrochloric acid, acetic acid,sulfuric acid or phosphoric acid. For example diazotization and couplingcan be carried out in the same reaction medium.

Alkali metal nitrites, such as, for example, sodium nitrite, in solidform or as an aqueous solution, or in nitrosylsulfuric acid are employedas the nitrosating agents. The preparation of the diazonium ion,typically through the reaction with excess nitrous acid or the like suchas nitrosyl sulfuric acid at low temperature to form the electrophilicion Aryl-N₂ ⁺ is published in the literature, e.g. in [Advanced OrganicChemistry, Fieser&Fieser, pages 736-740] or [Organische Chemie, K. PeterC. Vollhardt, pages 1154-1157, I. Auflage 1988].

The compound of formula (II), wherin X and Y signify hydrogen is known[V. F. Pozdnev, Khim Geterosikl. Soedin. 1990, 3, 312] and the compoundsof formulae (III) may easily be produced in a manner familiar to theperson skilled in the art. The compound of formula (II), wherein Xand/or Y signifie bromine group are synthesized analogously to example 1in DE 196 43 769 A1. The dyes of formula (I), wherein X and/or Y signifya cyano group are prepared analogously to example 1 of EP 554 695 A1 byexchange of the bromine by the —CN group.

The new dyestuffs of formula (I) as well as mixtures thereof can be usedfor dyeing and printing semisynthetic and, preferably, synthetichydrophobic fiber materials, especially textile materials. Textilematerials consisting of blended fabrics containing such semisynthetichydrophobic fiber materials can also be dyed or printed by means of thedyes of this invention.

Suitable semisynthetic textile materials are mainly cellulose-2½acetate, cellulose triacetate, polyamides and high molecular weightpolyesters as well as mixtures thereof with cellulose.

Synthetic hydrophobic textile materials consist mainly of lineararomatic polyester, for example of those consisting of terephthalic acidand glycols, in particular ethylene glycol or condensate of terephthalicacid and 1,4-bis(hydroxymethyl)cyclohexane; of polycarbonates, e.g.those consisting of α,α-dimethyl-4,4′-dihydroxydiphenylmethane andphosgene, and of fibers based on polyvinyl chloride and polyamide.

The hydrophobic synthetic materials can be in the form of sheet-like orthread-like structures, and can be processed, for example, to yarns orwoven, knitted or looped textile fabrics. The novel dyes are alsosuitable for dyeing hydrophobic synthetic material in the form of microfibers.

It is expedient to convert the novel dyes according to formula (I)before use into a dye formulation. This is done by milling the dye to anaverage particle size of 0.1 to 10 micron. Milling can be carried out inthe presence of dispersants. Typically, the wet dye is milled with adispersant, and thereafter dried under vacuum or by spray drying.Printing pastes and dyebaths can be prepared by adding water to theformulation so obtained.

The new dyestuffs according to formula (I) are applied to the textilematerials by known dyeing or printing methods, e.g. those described inFrench patent application No. 1.445.371.

Typically, polyester fiber materials are dyed from an aqueous dispersionby the exhaust process in the presence of customary anionic or non-ionicdispersants and in the presence or absence of customary swelling agents(carrier) in the temperature range from 65° C. to 140° C.

Cellulose-2½-acetate is preferably dyed at a temperature from 65° C. to85° C. and cellulose triacetate at temperatures up to 115° C. The noveldyes are suitable for dyeing by the thermosol process, for the exhaustprocess, the continuous process and for printing as for modern imagingprocesses, e.g. thermo-transfer printing, ink-jet printing, hot meltinkjet printing or by conventional printing processes.

The thermosol process, the exhaust process and the continuous processare well known dyeing processes and are described for example in M.Peter and H. K. Rouette: “Grundlagen der Textilveredelung; Handbuch derTechnologie, Verfahren und Maschinen”, 13^(th) revised Edition, 1989,Deutscher Fachverlag GmbH, Frankfurt am Main, Germany, ISBN3-87150-2774; wherein the following pages are of special interest: pages460-461, 482-495, 556-566 and 574-587.

In the inkjet printing process, individual droplets of the ink aresprayed from a nozzle onto a substrate in a controlled manner. Thecontinuous inkjet method and the drop-on-demand method are employedpredominantly for this purpose. In the case of the continuous inkjetmethod, the droplets are produced continuously and droplets not neededfor printing are diverted into a collecting vessel and recycled. In thecase of the discontinuous drop-on-demand method, by contrast, dropletsare generated and printed as desired, i.e. droplets are only generatedwhen this is necessary for printing. The droplets may be generated forexample by means of a piezo inkjet head or by means of thermal energy(bubble jet).

In hot melt inkjet printer solid hot melt inks are loaded in a printercapable of melting the ink in the inkjet printer head, ejecting theliquid ink which quickly resolidifies upon impacting a substrate.Conventional hot melt inkjet printers operate with a printing head andinkjet temperature of about 120 to about 150° C. At those temperatures,the solid ink is melted to a low viscosity liquid, generally about 8 to25 cP when measured at jetting temperature.

Conventional printing processes are well known and differ in the way theprinting ink or printing paste is transfered to the substrate: Forexample, inks or pastes can be applied by raised type (e.g. letterpress, flexographic), from a planar surface (lithographic), from arecessed surface (intaglio) or through a stencil (silk screen).Different methods of application and different substrates requiredifferent properties in the ink.

The dyeings are carried out from an aqueous liquor by the exhaustprocess, and the liquor ration can be chosen from a wide range, forexample from 1:4 to 1:100, preferably from 1:6 to 1:50.

The dyeing time is from 20 to 90 minutes, preferably from 30 to 60minutes. The dye liquors can additionally comprise other additives, forexample dyeing auxiliaries, dispersants, wetting agents and antifoams.

The liquor may also comprise mineral acids, such as sulfuric acid orphosphoric acid, or conveniently also organic acids, for example formicacid or acetic acid and/or salts, such as ammonium acetate, ammoniumsulfate or sodium sulfate. The acids mainly serve to adjust the pH ofthe dye liquors which is preferably in the range from 4 to 5.

The disperse dyes are usually present in the dye liquors in the form ofa fine dispersion. Suitable dispersants for the preparation of thisdispersion are e.g. anionic dispersants, such as aromatic sulfonicacid/formaldehyde condensates, sulfonated creosol oil/formaldehydecondensates, lignin sulfonates or copolymers of acrylic acid derivates,preferably aromatic sulfonic acid/formaldehyde condensates or ligninsulfonated, or nonionic dispersants based on polyalkylene oxidesobtainable, for examples, by polyaddition reaction from ethylene oxideor propylene oxide. Further suitable dispersants are listed in U.S. Pat.No. 4,895,981 or in U.S. Pat. No. 5,910,624.

Suitable inks or pastes comprise a) at least one dye of the formula (I)or mixtures of compounds of the formula (I), b) water or a mediumincluding a mixture of water and an organic solvent, an anhydrousorganic solvent or a solid having a low melting point, and c) optionallyfurther additives.

The inks or pastes preferably include a total amount of dyes of theabove formula (I), which is in the range from 1 to 35% by weight,especially in the range from 2 to 35% by weight, preferably in the rangefrom 2 to 30% by weight, more preferably in the range from 2.5 to 20% byweight, based on the total weight of the ink or paste. The inks include99-65% by weight, especially 98-65% by weight, preferably 98-70% byweight, more preferably 97.5-80% by weight, of an abovementioned mediumb), which includes water or a mixture of water and an organic solvent,an anhydrous organic solvent or a solid having a low melting point.

When said medium b) is a mixture including water and an organic solventor an anhydrous organic solvent, then the dye of formulae (I) ormixtures thereof are preferably completely dissolved in this medium.

Preferably the dye of formulae (I) or mixtures thereof have a solubilityof not less than 2.5% by weight in this medium b) 0 at 20° C.

When the ink composition of the invention is used for printing paperysubstrates or hydrophobic substrates made of acetate-, polyester-,polyamide-, polyacrylnitrile-, polyvinylchloride- orpolyurethane-polymers and blends thereof, the inks are preferably usedtogether with the following compositions.

When the medium is a mixture of water and an organic solvent, the weightratio of water to organic solvent is preferably in the range from 99:1to 1:99, more preferably in the range from 99:1 to 50:50, particularlypreferably in the range from 95:5 to 80:20. It is preferable for theorganic solvent which is included in the mixture with water to be awater-soluble solvent or a mixture of various water-soluble solvents.Preferred water-soluble or partly water soluble organic solvents areC₁₋₆-alcohols, preferably methanol, ethanol, n-propanol, isopropanol,n-butanol, sec-butanol, tert-butanol, n-pentanol, cyclopentanol andcyclohexanol; linear amides, preferably dimethylformamide ordimethylacetamide; ketones and keto alcohols, preferably acetone, methylethyl ketone, cyclohexanone and 4-hydroxy-4-methyl-2-pentanone;water-miscible ethers, preferably tetrahydrofuran and dioxane; diols,preferably diols possessing 2 to 12 carbon atoms, e.g. 1,5-pentanediol,ethylene glycol, propylene glycol, butylene glycol, pentylene glycol,hexylene glycol, thiodiglycol and oligo- and poly-alkylene glycols,preferably diethylene glycol, triethylene glycol, polyethylene glycoland polypropylene glycol; triols, preferably glycerol and1,2,6-hexanetriol; mono-C₁₋₄-alkyl ethers of diols, preferablymono-C₁₋₄-alkyl ethers of diols possessing 2 to 12 carbon atoms,particularly preferably 2-methoxyethanol, 2-(2-methoxyethoxy)ethanol,2-(2-ethoxyethoxy)ethanol, 2-[2-(2-methoxyethoxy)ethoxy]ethanol,2-[2-(2-ethoxyethoxy)ethoxy]ethanol and ethylene glycol monoallyl ether;cyclic amides, preferably 2-pyrrolidone, N-methyl-2-pyrrolidone,N-ethyl-2-pyrrolidone, caprolactam and 1,3-dimethylimidazolidone; cyclicesters, preferably caprolactone; sulphoxides, preferably dimethylsulphoxide and sulpholane.

In a preferred composition, the medium as per b) includes water and atleast 2 or more, more preferably 2 to 8, water-soluble organic solvents.

Particularly preferred water-soluble solvents are cyclic amides,particularly 2-pyrrolidone, N-methylpyrrolidone and N-ethylpyrrolidone;diols, preferably 1,5-pentanediol, ethylene glycol, thiodiglycol,diethylene glycol and triethylene glycol; and mono-C₁₋₄-alkyl anddi-C₁₋₄-alkyl ethers of diols, more preferably mono-C₁₋₄-alkyl ethers ofdiols possessing 2 to 12 carbon atoms, particularly preferably2-[2-(2-methoxyethoxy)ethoxy]ethanol.

A preferred medium as per b) includes:

-   -   (i) 75 to 95 parts by weight of water and    -   (ii) 25 to 5 parts of one or more of the following solvents:        diethylene glycol, 2-pyrrolidone, thiodiglycol,        N-methylpyrrolidone, cyclohexanol, caprolactone, caprolactam and        1,5-pentanediol,

wherein the parts are by weight and all parts of (i) and (ii) add up to100.

Examples of further useful ink compositions including water and one ormore organic solvents are found in the Patent Specifications U.S. Pat.No. 4,963,189, U.S. Pat. No. 4,703,113, U.S. Pat. No. 4,626,284 and EP425150A.

When the medium as per b) includes an anhydrous (i.e. less than 1% byweight of water) organic solvent, this solvent will have a boiling pointof 30 to 200° C., more preferably of 40-150° C., particularly preferablyof 50-125° C.

The organic solvent can be water-insoluble, water-soluble or mixtures ofsuch solvents. Preferred water-soluble organic solvents are allabove-described water-soluble organic solvents and mixtures thereof.

Preferred water-insoluble solvents include inter alia aliphatichydrocarbons; esters, preferably ethyl acetate; chlorinatedhydrocarbons, preferably CH₂Cl₂; and ethers, preferably diethyl ether;and mixtures thereof.

When the liquid medium as per b) includes a water-insoluble organicsolvent, it is preferable to add a polar solvent to increase thesolubility of the dye in the liquid medium.

Examples of such polar solvents are C₁₋₄-alcohols, preferably ethanol orpropanol; ketones, preferably methyl ethyl ketone.

The anhydrous organic solvent can consist of a single solvent or amixture of 2 or more different solvents.

When it is a mixture of different solvents, a mixture including 2 to 5different anhydrous solvents is preferred. This makes it possible toprovide a medium as per b) which permits good control of the dryingproperties and of the stability of the ink composition in storage.

Ink compositions including an anhydrous organic solvent or mixturesthereof are of particular interest when rapid drying times are requiredand especially when they are used for prints on hydrophobic andnon-absorbing substrates, such as plastic, metal and glass.

Preferred low-melting media have a melting point of 60 to 140° C. Usefullow-melting solids include long-chain fatty acids or alcohols,preferably those having a C₁₈₋₂₄-carbon chain, and sulphonamides.Conventional low-melting ink vehicles generally include variousproportions of waxes, resins, plasticizers, tackifiers, viscositymodifiers and antioxidants.

The ink composition and the printing pastes of the invention may furtherinclude as auxiliaries additional components which are normally used ininkjet inks or printing pastes, for example buffers, viscosityimprovers, surface tension improvers, fixation, accelerants, biozides,corrosion inhibitors, levelling agents, drying agents, humefactants, inkpenetration additives, light stabilisers, UV absorbers, opticalbrighteners, coagulation reducers, ionic or nonionic surfactants andconducting salts.

These auxiliaries are preferably added in an amount of 0-5% by weight toinks. To printing pastes up to 70% by weight, especially up to 60% byweight, preferably up to 55% by weight, based on the total weight of theprinting paste.

To prevent precipitations in the ink compositions of the invention, thedyes used have to be purified clean. This can be done with commonlyknown purifying methods.

When the compositions of the invention are used for printing textilefibre materials, preference is given to using the followingcompositions.

When printing textile fibre materials, useful additives, besides thesolvents including water, are synthetic thickener, natural thickener ormodified natural thikeners which may include water-soluble nonioniccellulose ethers, alginates or bean gum ether. All, the water-solublenonionic cellulose ethers, the alginates and the bean gum ether, areused as thickeners to adjust the ink to a certain viscosity.

Useful water-soluble nonionic cellulose ethers include for examplemethyl-, ethyl-, hydroxyethyl-, methylhydroxyethyl-, hydroxypropyl- orhydroxypropylmethyl-cellulose. Preference is given to methylcellulose orin particular hydroxyethylcellulose. Cellulose ethers are customarilyused in the ink in an amount of 0.01 to 2% by weight, especially 0.01 to1% by weight, preferably 0.01 to 0.5% by weight, based on the totalweight of the ink.

Useful alginates include in particular alkali metal alginates,preferably sodium alginate. These are customarily used in the ink in anamount of 0.01 to 2% by weight, especially 0.01 to 1% by weight,preferably 0.01 to 0.5% by weight, based on the total weight of the ink.

Printing pastes include up to 70% by weight thickening agents,preferably up to 55% by weight thickening agents. In printing pastes thethickening agents are used in an amount of 3 to 70% by weight,especially 5 to 60% by weight, preferably 7 to 55% by weight, based onthe total weight of the printing paste.

In the ink jet printing process preference is given to ink compositionshaving a viscosity of 1 to 40 mPa·s, especially 5 to 40 mPa·s,preferably 10 to 40 mPa·s. Ink compositions having a viscosity of 10 to35 mPa·s are particularly preferred.

Preference is given to ink compositions having a surface tension of15-73 mN/m, especially 20-65 mN/m, particularly preferably 30-50 mN/m.

Preference is given to ink compositions having a conductivity of 0.1-100mS/cm, especially 0.5-70 mS/cm, particularly preferably 1.0-60 mS/cm.

The inks may further include buffer substances, for example acetate,phospate, borax, borate or citrate. Examples are sodium acetate,di-sodium hydrogen phosphate, sodium borate, sodium tetraborate andsodium citrate.

The dyeings or printings thus obtained, have good all-round fastness;particularly noticeable are the thermo-migration fastness,thermo-fixation-, and pleating fastness, as well as the excellent wetfastness.

The dyestuffs of the present invention are useful for pigmentingmacromolecular organic materials of natural or synthetic origin, forexample plastics, resins, varnishes, paints, electrophotographic tonersand developers, electret materials, colour filters and also inks,including printing inks, and seed.

Macromolecular organic materials pigmentable using the dyestuffs of thepresent invention include for example cellulose compounds, such as forexample cellulose ethers and esters, such as ethylcellulose,nitrocellulose, cellulose acetates or cellulose butyrates, naturalbinders, such as for example fatty acids, fatty oils, resins and theirconversion products, or synthetic resins, such as polycondensates,polyadducts, addition polymers and copolymers, such as for example aminoresins, especially urea- and melamine-formaldehyde resins, alkyd resins,acrylic resins, phenoplasts and phenolic resins, such as novolaks orresols, urea resins, polyvinyls, such as polyvinyl alcohols, polyvinylacetals, polyvinyl acetates or polyvinyl ethers, polycarbonates,polyolefins, such as polystyrene, polyvinyl chloride, polyethylene orpolypropylene, poly(meth)acrylates and their copolymers, such aspolyacrylic esters or polyacrylonitriles, polyamides, polyesters,polyurethanes, coumarone-indene and hydrocarbon resins, epoxy resins,unsaturated synthetic resins (polyesters, acrylates) having differentcuring mechanisms, waxes, aldehydic and ketonic resins, gum, rubber andits derivatives and latices, casein, silicones and silicone resins;individually or in mixtures.

It is immaterial in this connection whether the macromolecular organiccompounds mentioned are present as plastically deformable compositions,melts or in the form of dopes, dispersions, varnishes, paints orprinting inks. Depending on the intended application, it will beadvantageous to use the dyestuffs of the present invention as a blend orin the form of preparations or dispersions. Based on the macromolecularorganic material to be pigmented, the dyestuffs of the present inventionare used in an amount of 0.05% to 30% by weight and preferably 0.1% to15% by weight.

Instead of a ground and/or finished pigment composition of the presentinvention it is in some cases also possible to use a corresponding crudehaving a BET surface area of more than 2 m²/g and preferably more than 5m²/g. This crude can be used for the production of colour concentratesin liquid or solid form in concentrations of 5% to 99% by weight, aloneor optionally mixed with other crudes or ready-produced pigments.

The dyestuffs of the present invention are also useful as colorants inelectrophotographic toners and developers, such as for example one- ortwo-component powder toners (also known as one- or two-componentdevelopers), magnetic toners, liquid toners, addition polymerizationtoners and also speciality toners.

Typical toner binders are addition polymerization, polyaddition andpolycondensation resins, such as styrene, styrene-acrylate,styrene-butadiene, acrylate, polyester, phenol-epoxy resins,polysulphones, polyurethanes, individually or in combination, and alsopolyethylene and polypropylene, which may each include furtheringredients, such as charge control agents, waxes or flow assistants, orare subsequently modified with these additives.

The dyestuffs of the present invention are further useful as colorantsin powders and powder coatings, especially in triboelectrically orelectrokinetically sprayable powder coatings used for surface coating ofobjects composed for example of metal, wood, plastic, glass, ceramic,concrete, textile material, paper or rubber.

Powder coating resins used are typically epoxy resins, carboxyl- andhydroxyl-containing polyester resins, polyurethane and acrylic resinstogether with customary hardeners. Combinations of resins are also used.For instance, epoxy resins are frequently used in combination withcarboxyl- and hydroxyl-containing polyester resins. Typical hardenercomponents (depending on the resin system) include for example acidanhydrides, imidazoles and also dicyandiamide and derivatives thereof,blocked isocyanates, bisacylurethanes, phenolic and melamine resins,triglycidyl isocyanurates, oxazolines and dicarboxylic acids.

The present invention is also directed to an optical layer comprising atleast one dye compound of formula (I) or mixtures thereof. The presentinvention is further directed to a method for producing optical layers acomprising the following steps

-   -   (a) providing a substrate    -   (b) dissolving a dye compound or a mixture of dye compounds of        formula (I) or mixtures thereof in an organic solvent to form a        solution,    -   (c) coating the solution (b) on the substrate (a);    -   (d) evaporating the solvent to form a dye layer.

Different methods may be employed for coating the solution (b) on thesubstrate (a). To provide for a thin and uniform film of the opticallayer, the material is usually deposited by spin coating, vacuumevaporation, jet coating, rolling coating or soaking.

The organic solvent is selected from C₁₋₈ alcohol, halogen substitutedC₁₋₈ alcohols, C₁₋₈ ketone, C₁₋₈ ether, halogen substituted C₁₋₄ alkane,or amides. Preferred alcohols C₁₋₈ alcohols or halogen substituted C₁₋₈alcohols are selected from methanol, ethanol, isopropanol, diacetonealcohol (DAA), 2,2,3,3-tetrafluoropropanol, trichloroethanol,2-chloroethanol, octafluoropentanol or hexafluorobutanol; the preferredC₁₋₈ ketones are selected from acetone, methylisobutylketone,methylethylketone, or 3-hydroxy-3-methyl-2-butanone; the preferredhalogen substituted C₁₋₄ alkanes are selected from chloroform,dichloromethane or 1-chlorobutane; and the preferred amides are selectedfrom dimethylformamide or dimethylacetamide.

In a preferred embodiment of the optical layer the optical layer is anoptical data recording layer which forms part of an optical datarecording media.

The construction of optical data recording media is known in the art. Anoptical data recording media generally comprises a substrate and arecording layer, the optical layer. Usually discs or wavers of organicpolymeric materials are used as substrates. Thus preferred substratesaccording to the invention are polycarbonate (PC) orpolymethylmethacrylate (PMMA). The substrate has to provide an even anduniform surface of high optical quality. The optical layer is depositedthereon in a thin and uniform film of high optical quality and definedthickness. Finally, a reflective layer, e.g. aluminium, gold or copper,is deposited upon the optical layer.

Advanced optical data recording media may comprise further layers, suchas protective layers, adhesive layers or additional optical layers.

For the application as optrical data recording layer the spin coatingprocess is the preferred method for coating the solution (b) on thesubstrate (a)

The present invention relates to the use of formula (I) in opticallayers for optical data recording, preferably for optical data recordingusing a laser with a wavelength up to 500 nm.

The invention further relates to a write only read many (WORM) typeoptical data recording medium capable of recording and reproducinginformation with radiation of blue laser, which employs compoundsaccording to formula (I) in the optical layer.

In the following examples, the parts and percentages are by weight. Thetemperatures are given in degrees Celsius.

EXAMPLE 1

Diazotization:

17.5 parts of 7-amino-4-methylcoumarin are dissolved in 100 parts ofwater and 36.5 parts of 30% HCl, 75 parts of ice are added andafterwards during a period of 1 hour 6.9 parts of sodium nitrite as anaqueous solution (40%) are added at a temperature of 0-5° C. Thesolution is stirred for 2 hours at 0- 5° C. and 0.1 part ofaminosulfonic acid are added to destroy the excess of sodium nitrite.

Coupling:

The previously prapared diazonium salt solution is added continuously toa solution of 20.6 parts of1-N-butyl-3-cyano-6-hydroxy-4-methyl-pyridon-2 in 400 parts water at atemperature of 15-25° C. The suspension is stirred for 1 h at 25° C. andthe pH is adjusted to 4 by addition of 10 parts of 30% sodium hydroxidesolution. The suspension is stirred again for 1 h and the precipitateddyestuff is filtered off, washed with water and dried in the vacuum at60° C.

The isolated dyestuff of formula (IV)

has a λ_(max) of 449 nm (in DMF) and dyes polyester in yellow shadeswith good fastness properties.

EXAMPLE 2

Diazotization:

The diazotization is done analogously as in Example 1. The previouslyprapared diazonium salt solution is added continuously to a solution of10.3 parts of 1-N-butyl-3-cyano-6-hydroxy-4methyl-pyridon-2 and 9.6parts of —N-propyl-3-cyano-6-hydroxy-4-methyl-pyridon-2 in 400 partswater at a temperature of 15-25° C. The suspension is stirred for 1 h at25° C. and the pH is adjusted to 4 by addition of 10 parts of 30% sodiumhydroxide solution. The suspension is stirred again for 1 h and theprecipitated dyestuff is filtered off, washed with water and dried inthe vacuum at 60° C.

The isolated dyestuff mixture of formula (V-A) and (V-B)

has a λ_(max) of 449 nm (in DMF) and dyes polyester in yellow shadeswith good fastness properties.

Table 1, 2 and 3 below, give further dyestuffs of formula (I-A), (I-B)and (I-C), which are produced analogously to the procedures given in thepreceding example.

All dyestuffs dye polyester fiber material with very good all-roundfastness, especially fastness to light, sublimation and wet fastness.TABLE 1 Examples 3-31 (I-A)

Ex. λ_(max) DMF No. X Y R⁴ R³ R² R¹ [nm] 3 H H H H —CH₂CH₃ —CH₂CH₂—CN455 4 H H H —CH₃ —CH₂CH₃ —CH₂CH₂—CN 467 5 H H H —CH₃ —CH₃ —CH₂CH₂—CN 4626 H H H H —CH₂—CH═CH₂ —CH₂CH₂—CN 460 7 H H H H —CH₂C≡CH —CH₂CH₂—CN 451 8H H H H —CH₂CH(OH)CH₃ —CH₂CH₂—CN 456 9 H H H H —CH₂CH₂OCOCH₃—CH₂CH₂OCOCH₃ 451 10 H H H H —CH₂CH₂COOCH₃ —CH₂CH₂COOCH₃ 449 11 H H H—NHCOCH₃ —CH₂CH₂OCOCH₃ —CH₂CH₂CN 476 12 H H H —NHCOCH₃ —CH₂CH₂OCOCH₃—CH₂CH₂OCOCH₃ 486 13 H H H —NHCOCH₃ —CH₂CH₃ —CH₂CH₃ 506 14 Br Br H—NHCOCH₃ —CH₂CH₃ —CH₂CH₃ 554 15 Br CN H —NHCOCH₃ —CH₂CH₃ —CH₂CH₃ 576 16H H H —NHCOCH₃ —CH₂CH₃ —CH₂—CH═CH₂ 501 17 H H H —NHCOCH₃ —CH₂CH₃—CH₂—C₆H₅ 499 18 H H H —NHCOCH₃ —CH₂CH₂OCH₃ —CH₂CH₂OCH₃ 502 19 H H H—NHCOC₂H₅ —CH₂CH₃ —CH₂CH₂OC₂H₅ 503 20 H H H —NHCOCH₃ —CH₂CH₃—CH₂CH₂COOCH₃ 498 21 H H H —NHCOCH₂Cl —CH₂CH₃ —CH₂CH₃ 502 22 H H H—NHCOCH₂CH₂Cl —CH₂CH₃ —CH₂CH₃ 503 23 H H H —NHCOCOOC₂H₅ —CH₂CH₃ —CH₂CH₃501 24 H H H —NHCOCOOCH₃ —CH₂CH₃ —CH₂CH₃ 500 25 H H H —NHCOCH₂OCH₃—CH₂CH₃ —CH₂CH₃ 503 26 H H H —NHCOCH₃ —CH₂CH₃ —CH₂CH₂COOCH₂COOCH₃ 495 27H H H —NHCOCH₃ —CH₂CH₃ —CH₂CH₂COOCH₂COOC₂H₅ 496 28 H H H —NHCOCH₃—CH₂CH₃ —CH₂CH₂COOCH₂C₆H₅ 493 29 H H H —NHCOCH₃ —CH₂CH₃—CH₂CH₂COOCH₂COC₆H₅ 490 30 H H H —NHCOCH₃ —CH₂CH₃—CH₂CH₂COOC₂H₄—N—phthalimidyl 497 31 H H H —CH₃ —CH₂—CH═CH₂ —CH₂CH₂—CN460

TABLE 2 Examples 32-41 (I-B)

Ex. λ_(max) DMF No. X Y R⁷ [nm] 32 H H —CH₃ 446 33 H H —CH₂CH₃ 448 34 HH —CH₂CH₂—CH₃ 449 35 H H —CH₂CH₂CH₂CH₂CH₂CH₃ 449 36 H H—CH₂CH₂CH₂—O—CH₂CH₂CH₂CH₃ 448 37 H H —CH₂—C₆H₅ 449 38 H H —CH₂CH₂—OH 44839 H H —CH₂CH₂COOCH₃ 449 40 H H —CH₂COOCH₃ 449 41 H H —NH—C₆H₅ 449

EXAMPLE 42

Diazotization:

17.5 parts of 7-amino4-methylcoumarin are dissolved in 100 parts ofacetic acid at a temperature of 15° C. and 17.4 parts of 40% nitrosylsulfuric acid are added within 15 minutes. The solution is stirred for 2hours at 15° C.

Coupling:

The previously prapared diazonium salt solution is added continuously toa solution of 17.4 parts of 3-methyl-1-phenyl-5-pyrazolone in 100 partsof N-methyl-pyrolidone and 50 parts of water containing 0.5 parts ofaminosulfonic acid at a temperature of 15-25° C. The suspension isstirred for 1 h at 25° C. Then 100 parts of ice are added. Thesuspension is stirred for 30 minutes, the dyestuff suspension isfiltered off, washed with water and dried in the vacuum at 60° C.

The isolated dyestuff of formula (VI)

has a λ_(max) of 411 nm (in DMF) and dyes polyester in yellow shadeswith good fastness properties. TABLE 3 Examples 42-65 (I-C)

Ex. λ_(max) DMF No. X Y R⁹ R⁸ [nm] 42 H H CH₃ —C₆H₅ 411 43 H H C₂H₅—C₆H₅ 413 44 H H CF₃ —C₆H₅ 467 45 H H CH₂CH₂CH₃ —CH₃ 407 46 H H CH₃ —H427 47 H H CH₃ —C₆H₄-2-CH₃ 413 48 H H CH₃ —C₆H₄-3-CH₃ 412 49 H H CH₃—C₆H₄-4-CH₃ 414 50 H H CH₃ —C₆H₄-2-OCH₃ 411 51 H H CH₃ —C₆H₄-3-OCH₃ 41252 H H CH₃ —C₆H₄-4-OCH₃ 410 53 H H CH₃ —C₆H₄-2-OH 409 54 H H CH₃—C₆H₄-3-OH 411 55 H H CH₃ —C₆H₄-4-OH 412 56 H H CH₃ —C₆H₄-2-COOH 410 57H H CH₃ —C₆H₄-3-Cl 410 58 H H CH₃ —C₆H₄-4-COOC₂H₅ 412 59 H H COOC₂H₅—C₆H₅ 437 60 H H CH₃ —CH₂CHOHCH₃ 405 61 H H CH₃ —CH₂CHOHC₂H₅ 407 62 H HCH₃ —cyclo-hexyl 404 63 H H CH₃ —C₆H₄-4-SO₂C₂H₄OH 414 64 H H CH₃—C₆H₄-4-NO₂ 418 65 H H CH₃ —COCH₃ 435

APPLICATION EXAMPLE A

17.5 parts of the dyestuff according to example 1 in the form of themoist presscake are wet-ground by a known method with 32.5 parts of acommercial dispersing agent based on lignin sulfonates, and pulverizedto a powder. 1.2 parts of this dye preparation are added to 2000 partsof demineralized water of 70° C., which contains 40 parts of ammoniumsulfate; the pH value of the dye bath is set at 5 with 85% formic acid.100 parts of washed polyester fiber fabric are placed in this dye bath,the container is closed, heated to 130° C. over the course of 20minutes, and dyeing continues for a further 60 minutes at thistemperature. After cooling, the polyester fiber fabric is removed fromthe dye bath, rinsed, soaped and cleaned by reduction with sodiumhydrosulfite in the usual way. After thermo-fixation (180° C., 30 sec),a yellow dyeing is obtained with very good all-round fastness,especially fastness to light and sublimation, in particular excellentwet fastness. The dyestuffs of examples 2 to 65 may be used in analogousmanner, and dyeings with very good all-round fastness are obtained.

Dyeing polyester yarn can be carried out analogously with examples 2 to65.

APPLICATION EXAMPLE B

2.5 parts of the dyestuff obtained in Example 1 are dissolved withstirring at 25° C. in a mixture of 20 parts diethyleneglycol and 77.5parts water to obtain a printing ink suitable for ink jet printing.

The dyestuffs of examples 2 to 65 or dyestuff mixtures of Examples 1 to65 can also be used in a manner analogous to that described inApplication Example B.

APPLICATION EXAMPLE C

A printing paste according to the invention consists of

-   500 g of a thickener (bean gum ether e.g. Indalca™),-   10 g of a fixation accelerant (e.g. Printogen HDN™),-   10 g of a levelling agent (e.g. Sandogen CN™),-   10 g of a buffer and dispersant system for dyeing (eg. Sandacid PB™;    1:2) and-   10 g of a dye of example 1-   and adding water up to 1000 g.

(Indalca was purchased from Cesalpinia S.p.A, Italy; Sandogen, Printogenand Sandacid are a trademarks of Clariant AG, Muttenz/Switzerland.)

This printing paste is used for printing papery substrates, textilefibre materials and plastic films and plastic transparencies.

The dyestuffs of examples 2 to 65 or dyestuff mixtures of Examples 1 to65 can also be used in a manner analogous to that described inApplication Example C.

APPLICATION EXAMPLE D

A polyester Interlock fabric was printed with a conventional printingmachine using the printing paste of the APPLICATION EXAMPLE C. Theresulting printed fabric is dried for 3 minutes at 110° C. and thentreated with hot steam for 7 minutes at 175° C. The fabric was rinsedwith cold tap water for 5 minutes, and then rinsed for 5 minutes withdemineralised water. The so treated fabric was reductively cleansed in abath comprising 4 g/l Na₂CO₃, 2 g/l hydrosulfite sodium salt (85%) and 1g/l Lyogen DFT™ (Trademark of Clariant AG, Muttenz, Switzerland).Further rinsing for 15 minutes with tap water was followed by a finaldrying step. This leaves a polyester fabric with a yellow print withvery good all-round fastness, especially fastness to light andsublimation and wet fastness.

The dyestuffs of examples 2 to 65 or dyestuff mixtures of Examples 1 to65 can also be used in a manner analogous to that described inApplication Example D.

APPLICATION EXAMPLE E

The ink jet printing composition is preferably prepared by heating themedium to 40° C. and then adding a dye of the example 1. The mixture isstirred until the dyes are dissolved. The composition is then cooleddown to room temperature and the further ingredients are added.

The fractions of the individual components of the ink compositions

-   6 parts of the dye of example 1,-   20 parts of glycerol and-   74 parts of water.

This ink composition is used for printing papery substrates, textilefibre materials and plastic films and plastic transparencies.

The dyestuffs of examples 2 to 65 or dyestuff mixtures of Examples 1 to65 can also be used in a manner analogous to that described inApplication Example E.

APPLICATION EXAMPLE F

A polyester Interlock fabric was ink jet printed using the printing inkof the APPLICATION EXAMPLE E. The printed fabric was treated analouguslyto the post printing treatment of APPLICATION EXAMPLE D. This leaves apolyester fabric with a yellow print with very good all-round fastness,especially fastness to light and sublimation, in particular excellentwet fastness.

The dyestuffs of examples 2 to 65 or dyestuff mixtures of Examples 1 to65 can also be used in a manner analogous to that described inApplication Example F.

1. A dyestuff or a mixture of dyestuffs of formula (I)

wherein X is H; halogen, —CN; —SO₂CH₃; —OH; —OCH₃ or —NO₂, Y is H;halogen, or —CN, and K is a coupling component radical of the6-hydroxypyridone-2, aniline, a-naphthylamine, 5-aminopyrazole,5-hydroxypyrazole, indole, tetrahydrochinoline, 2-aminothiazole,2-aminothiophene, phenole which is not 3,5-dimethyl substituted and thesubstituents in the 3 and 5 position are not members of a second ring,2-naphthol, benzomorpholine or 2,6-diaminopyridine series.
 2. A dyestuffor mixture of dyestuffs according to claim 1 of formula (I-B)

wherein X is H; halogen, —OH; —OCH₃ or NO₂ Y is H, R⁷ is H; benzyl;phenyl; C₁₋₆-alkyl; substituted C₂₋₄-alkyl,—C₁₋₂-alkylene-COOC₁₋₂-alkyl; —NHC₆H₅ or —NH₂.
 3. A dyestuff or mixtureof dyestuffs according to claim 1 of formula (I-A)

wherein X is H; halogen, —CN, —OH; —OCH₃ or —NO₂, Y is H; halogen, or—CN, and R¹ is C₁₋₆-alkyl; substituted C₂₋₄-alkyl, C₃₋₄-alkenyl;substituted C₃₋₄-alkenyl, C₃₋₄-alkinyl, C₂₋₄-alkylene-OCO—C₁₋₃-alkyl;C₂₋₄-alkylene-O(CO)O—C₁₋₃-alkyl; C₁₋₃alkylene-COO—R⁵;—C₁₋₃-alkylene-COO—C₂₋₃-alkylene-N-phthalimid; C₁₋₃-alkylene-COOCH₂COOR⁵or C₁₋₃-alkylene-COOCH₂COR⁶, R⁵ is C₁₋₄-alkyl; C₁₋₂-alkoxyethyl;C₃₋₄-alkenyl; C₃₋₄-alkinyl; cinnamyl; phenoxyethyl; phenyl-C₁₋₃alkyl;tetrahydrofurfuryl-2; phenyl or phenyl substituted by —CH₃, —OCH₃,—COOCH₃ or —COOC₂H₅, R⁶ is C₁₋₄-alkyl; phenyl or substituted phenyl, R²is H; C₁₋₆-alkyl; substituted C₂₋₄-alkyl, C₃₋₄-alkenyl; substitutedC₃₋₄-alkenyl, C₃₋₄-alkinyl, C₂₋₄-alkylene-OCO—C₁₋₃-alkyl orC₁₋₃alkylene-COO—R⁵, R³ is H; CH₃; —NHCO-A¹ or —NHCOO-A², wherein A¹ isH; C₁₋₄-alkyl; C₂₋₃-alkenyl; phenyl; —NH₂ or substituted C₁₋₂-alkyl, A²is C₁₋₄-alkyl or substituted C₂₋₄-alkyl, and R⁴ is H; halogen orC₁₋₄alkoxy.
 4. A dyestuff of mixture of dyestuffs according to claim 1of formula (I-C)

wherein X is H; halogen, —OH; —OCH₃ or NO₂; Y is H, R⁸ is H; C₁₋₆-alkyl;cyclo-hexyl; phenyl; substituted phenyl, R⁹ is C₁₋₄-alkyl; phenyl or—CF₃.
 5. A process for the production of a dyestuff of formula (I),according to claim 1 comprising the step of coupling a diazotized amineof formula (II)

with an amine of formula (III)H—K   (III)
 6. A dyed or printed fiber or thread dyed with a dyestuff ora mixture of dyestuffs according to claim 1, wherein the fiber or threadcomprise, fully or semi-synthetic, hydrophobic, organic materials.
 7. Aninkjet for an inkjet printing process or hot melt inkjet processcomprising a dyestuff or mixture of dyestuffs according to claim
 1. 8. Acomposition comprising a dyestuff or a mixture of dyestuffs according toclaim
 1. 9. The composition according to claim 8 wherein the compositionis a printing paste, a printing ink, an inkjet printing ink or a hotmelt inkjet printing ink.
 10. Fibers or threads or materials producedthereof, wherein the fibers or threads comprise fully or semi-synthetic,hydrophobic, organic materials dyed or printed with a dyestuff or amixture of dyestuffs as claimed in claim
 2. 11. A dyestuff or mixture ofdyestuffs according to claim 1, wherein X is Cl or Br.
 12. A dyestuff ormixture of dyestuffs according to claim 1, wherein Y is Cl or Br.
 13. Adyestuff or mixture of dyestuffs according to claim 2, wherein X is Clor Br.
 14. A dyestuff or mixture of dyestuffs according to claim 2,wherein the substituted C₂₋₄-alkyl is substituted by one substituentselected from the group consisting of halogen, —CN, —OH, —OC₁₋₄-alkyl,—OCOC₁₋₂-alkyl, —OC₆H₅ and —C₆H₅.
 15. A dyestuff or mixture of dyestuffsaccording to claim 3, wherein X is Cl or Br.
 16. A dyestuff or mixtureof dyestuffs according to claim 3, wherein Y is Cl or Br.
 17. A dyestuffor mixture of dyestuffs according to claim 3, wherein substitutedC₂₋₄-alkyl of R¹ is substituted by one or more substituents selectedfrom the group consisting of halogen, —CN, —SCN —OC₁₋₄-alkyl,—OCOC₁₋₃-alkyl, —OCHO, —OC₆H₅ and —C₆H₅.
 18. A dyestuff or mixture ofdyestuffs according to claim 3, wherein the substituted C₃₋₄-alkenyl ofR¹ is substituted by —Cl or —Br.
 19. A dyestuff or mixture of dyestuffsaccording to claim 3, wherein the C₃₋₄-alkinyl of R¹ is propargyl.
 20. Adyestuff or mixture of dyestuffs according to claim 3, wherein thesubstituted phenyl of R⁶ is substituted by one or more substituentsselected from the group consisting of —CH₃, —OCH₃, —OC₂H₅, halogen and—OH.
 21. A dyestuff or mixture of dyestuffs according to claim 3,wherein the substituted C₂₋₄-alkyl of R² is substituted by one or moresubstituents selected from the group consisting of halogen, —CN, —OH,—OC₁₋₄-alkyl, —OCOC₁₋₃-alkyl, —OC₆H₅ and —C₆H₅.
 22. A dyestuff ormixture of dyestuffs according to claim 3, wherein the substitutedC₃₋₄-alkenyl of R² is substituted by —Cl or —Br.
 23. A dyestuff ormixture of dyestuffs according to claim 3, wherein the C₃₋₄-alkinyl ofR² is propargyl.
 24. A dyestuff or mixture of dyestuffs according toclaim 3, wherein the substituted C₁₋₂-alkyl of A¹ is substituted by oneor more substituents selected from the group consisting of —OH, —Cl,—OCH₃, OC₂H₅ and —C₆H₅.
 25. A dyestuff or mixture of dyestuffs accordingto claim 3, wherein the substituted C₂₋₄-alkyl of A² is substituted byone substituents selected from the group consisting of —Cl, —OCH₃ and—OC₂H₅.
 26. A dyestuff or mixture of dyestuffs according to claim 4,wherein X is Cl or Br.
 27. A dyestuff or mixture of dyestuffs accordingto claim 4, wherein the substituted phenyl of R⁸ is substituted by onesubstituent selected from the group consisting of halogen, —CH₃, —CN,—OH, —OC₁₋₄-alkyl, —OCOC₁₋₂-alkyl, —COC₁₋₂-alkyl, —COOH, —SO₂C₂H₄OH and—NO₂.
 28. A material comprising the dyed or printed fiber or threadaccording to claim 6.